CN117820844A - Flame-retardant polyurethane grouting material and preparation method thereof - Google Patents
Flame-retardant polyurethane grouting material and preparation method thereof Download PDFInfo
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- CN117820844A CN117820844A CN202410251069.5A CN202410251069A CN117820844A CN 117820844 A CN117820844 A CN 117820844A CN 202410251069 A CN202410251069 A CN 202410251069A CN 117820844 A CN117820844 A CN 117820844A
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- grouting material
- polyurethane
- flame
- polyester polyol
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 136
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 105
- 239000004814 polyurethane Substances 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 96
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 77
- 239000004014 plasticizer Substances 0.000 claims abstract description 69
- -1 methoxy fatty acid Chemical class 0.000 claims abstract description 49
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 47
- 239000000194 fatty acid Substances 0.000 claims abstract description 47
- 229930195729 fatty acid Natural products 0.000 claims abstract description 47
- 239000003085 diluting agent Substances 0.000 claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 35
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 31
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 125000005442 diisocyanate group Chemical group 0.000 claims description 44
- 239000003381 stabilizer Substances 0.000 claims description 42
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 25
- 239000006260 foam Substances 0.000 claims description 24
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 36
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 26
- 239000011496 polyurethane foam Substances 0.000 abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000004872 foam stabilizing agent Substances 0.000 description 11
- 238000005187 foaming Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229920002545 silicone oil Polymers 0.000 description 11
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical group ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000008029 phthalate plasticizer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 2
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane materials, in particular to a flame-retardant polyurethane grouting material and a preparation method thereof. The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight: 20 parts of polyurethane prepolymer, 15-16 parts of plasticizer, 4-4.6 parts of diluent and 0.8-1 part of auxiliary agent; the mass ratio of the mixture of the methoxy fatty acid chloride and the dioctyl phthalate is 2-7:10. According to the invention, through the mutual matching of the polyester polyol in the polyurethane prepolymer and the methoxy chloride fatty acid ester in the plasticizer, the strength of the polyurethane foam is improved, the flame retardant effect is improved, and the problems of influence on the durability of the flame retardant effect and the strength of the polyurethane foam caused by exudation of phosphorus element due to the use of a phosphorus flame retardant are avoided.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a flame-retardant polyurethane grouting material and a preparation method thereof.
Background
The polyurethane grouting material has the advantages of strong permeability, good water blocking effect, good pourability, high consolidation strength and the like, so the polyurethane grouting material can be applied to solve the problems of uneven particle distribution, cracks, local settlement of building houses, water seepage and the like caused by rusting and corrosion of steel bars of the cement grouting material.
At present, the polyurethane grouting material mainly comprises a polyurethane prepolymer, a diluent and an auxiliary agent, wherein the polyurethane prepolymer is mainly prepared by reacting a diisocyanate compound and polyether polyol, the diluent is mainly propylene carbonate, the auxiliary agent mainly comprises a plasticizer, a catalyst and a flame retardant, the plasticizer is a phthalate plasticizer, the flame retardant is tris (2-chloroethyl) phosphate or tris-dichloropropyl phosphate, and the catalyst is an organotin catalyst. In the grouting process, the polyurethane prepolymer reacts with water and is bonded with the base material to form a high-strength polyurethane consolidated body, so that the effect of reinforcing and blocking water is achieved. Because propylene carbonate is inflammable, and the foamed polyurethane grouting material is of a porous structure, the density is low, and the flame retardance is poor, the flame retardant effect is improved by adding the flame retardant.
However, in the research process, the applicant finds that most of the flame retardant polyurethane grouting materials on the market adopt low molecular weight phosphate esters such as flame retardant tris (2-chloroethyl) phosphate (TCEP) and tris (2-chloropropyl) phosphate (TCPP), and the flame retardant has strong flame retardant effect, but is easy to migrate and volatilize from polyurethane foam after long-term use, so that the durability of the flame retardant effect is reduced; in addition, TCPP has a plasticizing effect, which is very likely to reduce polyurethane foam strength.
Disclosure of Invention
The invention aims to solve the problem that the flame retardant effect of the polyurethane grouting material and the strength of polyurethane foam are affected by the added phosphate flame retardant in the existing polyurethane grouting material, and provides an environment-friendly high-strength low-shrinkage flame retardant polyurethane grouting material and a preparation method thereof.
The invention aims to improve the existing polyurethane grouting material, and improve the strength and flame retardant effect of the polyurethane foam body while avoiding using phosphate flame retardants.
In order to achieve the above object, the technical scheme of the present invention is as follows.
The first aspect of the invention provides a flame-retardant polyurethane grouting material, which is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 15-16 parts of plasticizer, 4-4.6 parts of diluent and 0.8-1 part of auxiliary agent;
the plasticizer is a mixture of methoxy chloride fatty acid ester and dioctyl phthalate; the mass ratio of the mixture of the methoxy fatty acid chloride and the dioctyl phthalate is 2-7:10.
In a preferred embodiment, the polyurethane prepolymer is prepared by reacting a diisocyanate and a polyester polyol; wherein the mass ratio of the diisocyanate to the polyester polyol is 7-10:1.
In a preferred embodiment, the diisocyanate is a mixture of at least two of toluene diisocyanate, diphenylmethane diisocyanate, 4-methoxy-2-tolylene isocyanate, 4-isopropylisocyanate, isophorone diisocyanate.
In a preferred embodiment, the polyester polyol is a modified aromatic polyester polyol.
In a preferred embodiment, the polyester polyol has a hydroxyl number of 200 to 250 mg KOH/g.
In a preferred embodiment, the adjunct is a foam stabilizer and a catalyst; the foam stabilizer is a mixture of methyl silicone oil and white oil; the catalyst is pentamethyldiethylenetriamine.
In a preferred embodiment, the mass ratio of the foam stabilizer to the catalyst is 3.8-4:1-2.
In a preferred embodiment, the mass ratio of the methyl silicone oil to the white oil is 1:3-3.5.
In a preferred embodiment, the diluent is propylene carbonate polyol 7001 vacuum dehydrated at 110±5 ℃.
The second aspect of the invention provides a preparation method of the flame retardant polyurethane grouting material of the first aspect, comprising the following steps:
stirring isocyanate and polyester polyol at 80-85 ℃ for reaction to prepare polyurethane prepolymer;
and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent and the auxiliary agent to prepare the flame-retardant polyurethane grouting material.
In a preferred embodiment, the reaction time during the preparation of the polyurethane prepolymer is from 2 to 3 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through the mutual matching of the polyester polyol in the polyurethane prepolymer and the methoxy chloride fatty acid ester in the plasticizer, the strength of the polyurethane foam is improved, the flame retardant effect is improved, and the problems of the flame retardant effect and the foam strength are prevented from being influenced due to the volatilization loss of phosphorus element caused by using the phosphorus flame retardant.
2. According to the invention, the shrinkage rate of the polyurethane consolidated body is low by adjusting the proportion of the raw materials, and the anti-seepage and plugging durability of the consolidated body is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the prior art, the polyurethane grouting material consists of a polyurethane prepolymer, a diluent and an auxiliary agent, wherein the polyurethane prepolymer is prepared by reacting a diisocyanate compound and polyether polyol at 80-85 ℃, the diluent is propylene carbonate, the auxiliary agent comprises a plasticizer, a catalyst and a flame retardant, the plasticizer is a phthalate plasticizer, the flame retardant is tris (2-chloroethyl) phosphate or tris-dichloropropyl phosphate, and the catalyst is an organotin catalyst. Because propylene carbonate is inflammable, and the foamed polyurethane grouting material is of a porous structure, the density is low, and the flame retardance is poor, the flame retardant effect is improved by adding the flame retardant.
However, in the research process, the applicant finds that most of the flame retardant polyurethane grouting materials on the market adopt low molecular weight halogenated phosphate flame retardants such as flame retardant tris (2-chloroethyl) phosphate (TCEP), tris (2-chloropropyl) phosphate (TCPP) and the like, and the flame retardant has strong flame retardant effect, but is easy to migrate and volatilize from polyurethane foam after long-term use, so that the durability of the flame retardant effect is reduced; and when the added halogenated phosphate flame retardant is combusted in polyurethane, the flame retardant is decomposed to generate a large amount of smoke and corrosion-stimulating gas, which is not beneficial to environmental protection. The halogenated phosphate flame retardant has high volatility, poor heat resistance, relatively high price and easy influence of other factors on the use effect, and can be dropped in the combustion process. In addition, TCPP has a plasticizing effect, which is very likely to reduce polyurethane foam strength. Therefore, there is a need for improvements in the existing polyurethane grouting materials to improve the strength and flame retardant effect of polyurethane foam while avoiding the use of phosphate flame retardants.
In addition, the polyurethane grouting material disclosed in the prior art has shrinkage phenomenon, so that cracking and re-leakage are caused, and the anti-seepage and plugging durability is reduced. In order to improve the pourability of the polyurethane grouting material, volatile and low-flash-point toxic solvents such as acetone, dimethylbenzene and the like are often added to reduce the viscosity of the polyurethane grouting material. Not only pollutes the environment and has high fireproof requirement on construction sites, but also easily causes health hazard to the bodies of constructors.
Based on the above problems, the present invention aims to improve the flame retardant effect and avoid the problems of the volatilization loss of phosphorus element caused by the use of phosphorus flame retardant, the flame retardant effect and the foam strength by the mutual matching of polyester polyol in polyurethane prepolymer and methoxy chloride fatty acid ester in plasticizer, while improving the strength of polyurethane foam. The invention can reduce the shrinkage rate of the polyurethane consolidated body and improve the anti-seepage and leak-stopping durability of the polyurethane consolidated body by adjusting the proportion of the raw materials. The flame-retardant polyurethane grouting material disclosed by the invention not only comprises the performances of the existing product, but also has the advantages of high strength, low shrinkage, good lasting flame retardance, no volatile substances and high solid content of polyurethane foam.
The first aspect of the invention provides a flame-retardant polyurethane grouting material, which is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 15-16 parts of plasticizer, 4-4.6 parts of diluent and 0.8-1 part of auxiliary agent;
the plasticizer is a mixture of methoxy chloride fatty acid ester and dioctyl phthalate; the mass ratio of the mixture of the methoxy fatty acid chloride and the dioctyl phthalate is 2-7:10.
The mass ratio of the mixture of the methoxy fatty acid chloride and the dioctyl phthalate is 2-7:10. For example, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, etc.
The amount of the chlorinated methyl fatty acid ester influences the oxygen index of the polyurethane foam and has a flame retardant effect; in addition, it has a plasticizing effect, reduces the viscosity of the grouting material and affects the compressive strength of the polyurethane foam. The plasticizer molecules are inserted between polyurethane prepolymer molecular chains, so that acting force among the polyurethane prepolymer molecular chains is weakened, mobility of the polyurethane prepolymer molecular chains is increased, and the polyurethane prepolymer molecular chains can slide more freely, so that fluidity of the polyurethane grouting material is improved, crystallinity of the polyurethane prepolymer molecular chains is reduced, and plasticity of the polyurethane prepolymer is increased. The chlorinated methoxy fatty acid ester has the flame-retardant effect, and the polyester polyol in the polyurethane prepolymer and the chlorinated methoxy fatty acid ester in the plasticizer are mutually matched, so that the product structure is more compact, the ignition time of the polyurethane foam can be further delayed, and the flame-retardant effect of the polyurethane foam can be improved.
In a preferred embodiment, the polyurethane prepolymer is prepared by reacting a diisocyanate and a polyester polyol; wherein the mass ratio of the diisocyanate to the polyester polyol is 7-10:1. For example, 7:1, 8:1, 9:1, 10:1, etc.
In a preferred embodiment, the diisocyanate is a mixture of at least two of toluene diisocyanate (TDI, M20S diisocyanate), diphenylmethane diisocyanate (MDI), 4-methoxy-2-tolylene isocyanate, 4-isopropylisocyanate (IPPI), isophorone diisocyanate (IPDI).
In a preferred embodiment, the polyester polyol is a modified aromatic polyester polyol. For example, the polyester polyol model STEPANPOL PS-7001 is simply referred to as polyester polyol 7001.
The plasticizer can reduce intermolecular interaction force of polyurethane prepolymer and improve fluidity; the plasticizing effect of the methoxy chloride fatty acid ester in the plasticizer is excellent, and the plasticizer is nontoxic, environment-friendly and flame-retardant. Compared with non-inflammable polyurethane, the polyester polyol in the polyurethane prepolymer is modified aromatic polyester polyol, and can be matched with the methoxy chloride fatty acid ester in the plasticizer, so that the product structure is more compact, the ignition time of a polyurethane foam body can be further delayed, and the flame retardant effect is improved.
In a preferred embodiment, the polyester polyol has a hydroxyl number of 200 to 250 mg KOH/g.
In a preferred embodiment, the adjunct is a foam stabilizer and a catalyst; the foam stabilizer is a mixture of methyl silicone oil and white oil; the catalyst is pentamethyldiethylenetriamine. The catalyst mainly acts on the foaming reaction, so that the foaming reaction and the gel reaction reach an equilibrium state, and products with excellent performance are prepared.
In a preferred embodiment, the mass ratio of the foam stabilizer to the catalyst is 3.8-4:1-2; for example, 4:1, 3.8:1.2, 4:2, etc. In a preferred embodiment, the mass ratio of the methyl silicone oil to the white oil is 1:3-3.5; for example, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, etc.
In a preferred embodiment, the diluent is propylene carbonate.
The second aspect of the invention provides a preparation method of the flame retardant polyurethane grouting material of the first aspect, comprising the following steps:
stirring isocyanate and polyester polyol at 80-85 ℃ for reaction to prepare polyurethane prepolymer;
and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent and the auxiliary agent to prepare the flame-retardant polyurethane grouting material.
In a preferred embodiment, the reaction time during the preparation of the polyurethane prepolymer is from 2 to 3 hours.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
The methods described in the examples below are conventional, unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 2
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent consists of a stabilizer and a catalyst in a mass ratio of 3.8:1.2, mixing to obtain the final product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 3
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 0.8 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:2, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 4
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate in a mass ratio of 7:10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 5
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate in a mass ratio of 2: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 6
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 10:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 7
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 9:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Example 8
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 7:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
Comparative example 1
A flame retardant polyurethane grouting material is different from example 1 in that no catalyst is added. The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is a stabilizer, and the stabilizer is prepared from methyl silicone oil and white oil according to the mass ratio of 1:3, mixing.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, and base silicone oil and white oil as foam stabilizers; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent and the foam stabilizer according to the proportion.
Comparative example 2
A flame retardant polyurethane grouting material is different from example 1 in that a phosphate flame retardant TCPP is added, and polyether polyol 305 is used for replacing polyester polyol 7001 in example 1.
The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate, 1 part of auxiliary agent and 11 parts of phosphate flame retardant.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyether polyol 305, and the mass ratio of the diisocyanate M20S to the polyether polyol 305 is 8:1.
the plasticizer is prepared from methoxy fatty acid chloride and dioctyl phthalate according to the mass ratio of 6: 10.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The phosphate flame retardant is tris (2-chloropropyl) phosphate (TCPP).
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating polyether polyol 305 at 110+ -5deg.C, controlling water content to be less than or equal to 0.05%, and cooling to 60deg.C for use; and drying the reaction kettle, performing nitrogen replacement, adding diisocyanate M20S, gradually adding polyether polyol 305 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the flame retardant is prepared from methoxy chloride fatty acid ester and dioctyl phthalate serving as plasticizers, propylene carbonate serving as a diluent, base silicone oil and white oil serving as foam stabilizers, pentamethyl diethylene triamine serving as a catalyst, and tris (2-chloropropyl) phosphate (TCPP) serving as a phosphate flame retardant; the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer, the catalyst and the phosphate flame retardant are uniformly mixed according to the proportion.
Comparative example 3
A flame retardant polyurethane grouting material is different from example 1 in that a chlorinated methoxy fatty acid ester is not added. The flame-retardant polyurethane grouting material is prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 16 parts of plasticizer, 4 parts of propylene carbonate and 1 part of auxiliary agent.
The polyurethane prepolymer is prepared by reacting diisocyanate M20S and polyester polyol 7001, and the mass ratio of the diisocyanate M20S to the polyester polyol 7001 is 8:1.
the plasticizer is dioctyl phthalate.
The auxiliary agent is prepared from a stabilizer and a catalyst in a mass ratio of 4:1, mixing to obtain the product; the stabilizer is prepared from methyl silicone oil and white oil in a mass ratio of 1:3, and the catalyst is pentamethyldiethylenetriamine.
The preparation method of the flame-retardant polyurethane grouting material comprises the following steps:
1) Preparation of polyurethane prepolymer:
vacuum dehydrating the polyester polyol 7001 at 110+/-5 ℃, controlling the moisture content to be less than or equal to 0.05%, and cooling to 60 ℃ for standby; and drying the reaction kettle, carrying out nitrogen substitution, adding diisocyanate M20S, gradually adding polyester polyol 7001 in a stirring state, controlling the reaction temperature to be 80-85 ℃, reacting for 2 hours, and cooling after the reaction is finished to obtain the polyurethane prepolymer.
2) Preparing a flame-retardant polyurethane grouting material: the preparation method comprises the steps of taking methoxy chloride fatty acid ester and dioctyl phthalate as plasticizers, propylene carbonate as a diluent, base silicone oil and white oil as foam stabilizers, and pentamethyl diethylenetriamine as a catalyst; and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent, the foam stabilizer and the catalyst according to the proportion.
The performance test of the flame retardant polyurethane grouting material prepared in the above example was performed below to analyze the performance influence of different amounts on the flame retardant polyurethane grouting material.
Test 1: the different dosage proportions of the auxiliary agent have influence on the performance of the flame-retardant polyurethane grouting material.
Taking the materials prepared in examples 1-3 and comparative example 1, adding 5% of water, uniformly mixing, and then testing viscosity, setting time, nonvolatile content, foaming rate, specific gravity, compressive strength and oxygen index. The detection basis is as follows: JC/T2041-2020 polyurethane grouting material.
Table 1 different dosage and formulation of auxiliary
Note that: "-" means no catalyst was added.
Table 2 influence of different dosage ratios of the catalyst on the performance of the flame retardant polyurethane grouting material
Note that: the setting time is that of the flame retardant polyurethane grouting material plus 5% water.
The reaction process of the polyurethane foam is mainly divided into a gel reaction part and a foaming reaction part. If the foaming reaction is prior to the gel reaction, the viscosity is excessively slow, most of gas is generated before the gel reaction is completed, small bubbles are formed into large bubbles and escape, the physical properties such as strength of a foam product are affected by light weight, foam collapse in the reaction process is caused by heavy weight, and a non-uniform body with high density is obtained. If the gel reaction is faster than the foaming reaction, the viscosity increases too fast, and the material solidifies as the gel solidifies before enough bubbles are generated, resulting in a higher density of the plastic. As can be seen from the results of tables 1 and 2, the polyurethane reaction rate increased and the foaming rate increased with increasing catalyst amount.
In the above embodiments of the present invention, the catalyst is mainly used in the foaming reaction, so that the foaming reaction and the gel reaction reach an equilibrium state, and thus the product with excellent performance is obtained. The results of table 2 show that the different amounts of catalyst have a greater effect on the setting time of the flame retardant polyurethane grouting material, and that the setting time is prolonged by about 4 minutes without the catalyst in comparative example 1, as compared with example 1; the foaming rate of the flame retardant polyurethane grouting material is relatively reduced.
Test 2: the addition of the flame retardant affects the performance of the flame retardant polyurethane grouting material.
The flame retardant polyurethane grouting material (comparative example 2) prepared by adding a phosphate flame retardant under the composition of example 1 and replacing the polyester polyol 7001 of example 1 with the polyether polyol 305 was compared with the flame retardant polyurethane grouting material prepared by example 1 in performance. Performance test was performed according to the method of test 1 to verify the influence of the phosphate flame retardant on the mechanical properties of the prepared polyurethane grouting material.
TABLE 3 Effect of flame retardant addition on the Properties of flame retardant polyurethane grouting materials
As can be seen from the results of Table 3, comparative example 2 has a reduced nonvolatile content but a less different flame retardant effect after adding the flame retardant TCPP. Moreover, since the TCPP had a certain plasticity, the compressive strength of the polyurethane foam of comparative example 2 was lowered.
Test 3: the different dosage proportions of the chlorinated methoxy fatty acid ester affect the performance of the flame-retardant polyurethane grouting material
TABLE 4 dosage formulation of methoxy fatty acid esters chloride
Note that: mass ratio a The mass ratio of the methoxy fatty acid chloride to the dioctyl phthalate is shown.
"-" means that no chlorinated methoxy fatty acid ester was added.
TABLE 5 influence of the amount ratio of the methoxy fatty acid chloride on the performance of the flame retardant polyurethane grouting material
As can be seen from the results of tables 4 and 5, the amount of the chlorinated methyl fatty acid ester used affects the oxygen index of the polyurethane foam, and has a flame retardant effect; in addition, it has a plasticizing effect, reduces the viscosity of the grouting material and affects the compressive strength of the polyurethane foam.
The plasticizer molecules are inserted between polyurethane prepolymer molecular chains, so that acting force among the polyurethane prepolymer molecular chains is weakened, mobility of the polyurethane prepolymer molecular chains is increased, and the polyurethane prepolymer molecular chains can slide more freely, so that fluidity of the polyurethane grouting material is improved, crystallinity of the polyurethane prepolymer molecular chains is reduced, and plasticity of the polyurethane prepolymer is increased. The chlorinated methoxy fatty acid ester has the flame-retardant effect, and the polyester polyol in the polyurethane prepolymer and the chlorinated methoxy fatty acid ester in the plasticizer are mutually matched, so that the product structure is more compact, the ignition time of the polyurethane foam can be further delayed, and the flame-retardant effect of the polyurethane foam can be improved.
Test 4: the different dosage ratios of the polyester polyol 7001 have influence on the performance of the flame-retardant polyurethane grouting material
TABLE 6 dosage formulation of polyester polyol 7001
Note that: mass ratio a The mass ratio of the diisocyanate M20S and the polyester polyol 7001 in the polyurethane prepolymer is represented.
TABLE 7 influence of the amount ratio of the polyester polyol 7001 on the performance of the flame retardant polyurethane grouting material
As can be seen from the results of tables 6 and 7, the ratio of the polyurethane prepolymer was changed so that the setting time, viscosity, foaming ratio, specific gravity and compressive strength of the polyurethane were all affected to some extent.
In summary, the above embodiments of the present invention use propylene carbonate with high boiling point and low toxicity as the diluent, which ensures the pourability of the grouting liquid and is environment-friendly. The fire hazard of the grouting material in the production, transportation and construction processes can be reduced for a long time due to the adoption of the polyester polyol with low viscosity, high fireproof flame retardant property and thermal stability and the chlorinated methoxy fatty acid ester with flame retardant effect; the polyurethane foam generated by the reaction of the grouting material has flame retardance, so that the fire hazard of the environment where the polyurethane foam is used is reduced.
Compared with the addition of phosphorus flame retardant, the flame-retardant polyester polyol has the advantages that the obtained product has good stability and more compact structure, and can further delay the ignition time of the polyurethane foam body, thereby achieving the flame-retardant effect. Different from other phosphorus flame retardants, the flame-retardant polyester polyol has good heat resistance and compatibility, has small flame-retardant effect influenced by other factors, does not release harmful substances and produce dripping substances when being burnt by fire, and is more environment-friendly and safer; moreover, the strength of the polyurethane consolidated body is improved by adding the polyester polyol, and the shrinkage rate of the polyurethane consolidated body is low after proportioning and debugging, so that the anti-seepage and leak-stopping durability of the polyurethane consolidated body is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The flame-retardant polyurethane grouting material is characterized by being prepared from the following raw materials in parts by weight:
20 parts of polyurethane prepolymer, 15-16 parts of plasticizer, 4-4.6 parts of diluent and 0.8-1 part of auxiliary agent;
the plasticizer is a mixture of methoxy chloride fatty acid ester and dioctyl phthalate; the mass ratio of the mixture of the methoxy chloride fatty acid ester and the dioctyl phthalate is 2-7:10;
the polyurethane prepolymer is prepared by reacting diisocyanate and polyester polyol; the polyester polyol is modified aromatic polyester polyol;
the auxiliary agent is a foam stabilizer and a catalyst; the foam stabilizer is a mixture of methyl silicone oil and white oil; the catalyst is pentamethyldiethylenetriamine.
2. The flame retardant polyurethane grouting material of claim 1, wherein the mass ratio of diisocyanate to polyester polyol is 7-10:1.
3. The flame retardant polyurethane grouting material of claim 2, wherein the diisocyanate is a mixture of at least two of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate.
4. The flame retardant polyurethane grouting material of claim 1, wherein the hydroxyl value of the polyester polyol is 200-250 mg KOH/g.
5. The flame retardant polyurethane grouting material of claim 1, wherein the mass ratio of the foam stabilizer to the catalyst is 3.8-4:1-2.
6. The flame retardant polyurethane grouting material according to claim 1, wherein the mass ratio of the methyl silicone oil to the white oil is 1:3-3.5.
7. The flame retardant polyurethane grouting material of claim 1, wherein the diluent is propylene carbonate.
8. A method for preparing the flame retardant polyurethane grouting material of claim 1, comprising the following steps:
stirring isocyanate and polyester polyol at 80-85 ℃ for reaction to prepare polyurethane prepolymer;
and uniformly mixing the polyurethane prepolymer, the plasticizer, the diluent and the auxiliary agent to prepare the flame-retardant polyurethane grouting material.
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| CN111087649A (en) * | 2019-12-11 | 2020-05-01 | 中国平煤神马能源化工集团有限责任公司 | Coal-rock mass reinforcing composite plasticizer and application |
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